Residual hydrocarbon treatment



' tion which follows.

expansion of-the heated u ber, which chamber is maintained above -900 1"; in order to eiiect rapid variation ot any liquid4 .'material-,such'as V mayandusuallywillhe lmined with or latented .luly` 3l, t* u j uNlTlED ansmvat.

lohn Swarthnlore.y Pa., assigner to Process Corpora a.'y corporation oi Delaware aanwas-ima. par

, l ,u l (CLIM-55) This invention relates to processes of and apparatus for eiiectlng chemical reactions.k It is .y

especially adapted'to the treatmentor conversion `oi.' yresidues or'residualf materials such as those derived from petroleum, shale,roil, bitumi- `nous distillates, etc. -In one particular use, the Vinvention is concernedwith theonstream treatment oi' a residualhydrocarbon materiaLin a raction 'chamber and under .intense and controlled reaction conditions so astoremove there- 1 assist inf/the charge and to vaporizaubn' ofthe liquid einen or assist in controlling the time o! contact of the vapors .inl the reactionchamber, or inother words. ,to eilectrapid removal .ofj the vapors from thel chamber` in order to rminimire cracking ofthe vapors into lower boiling material suchy as. that. in` the l gasolineboilfrom all components such as ash'. coke. tarry and ,f:

` resinous material, asphalt and; other substances which would deleteriously aiiect `the use loi disv'tillate products ofthe process and'iollowln the 5 on-stream `operation the invention is, further concerned'with theeiiicient removal from the reaction chamber of the deleterious components which have deposited therein.. i f

One` object of the invention isto provide an improved Vmethod and apparatus,y Vfor preparing f deposit isremoved v l or `burning of thedeposit. The heat thusprovfrom heavy charging stocks, including bottomsA or residues, a clean distillate material whichmay be'sold commercially .without further treatment Y or which may itself be used as a' charging stockv Y 'for further operations, as in the production of lower boiling hydrocarbons, etc.vv Another object is to provide methodand apparatusrfor physi- 1 cally separating the deleterious .components or. coky material out ofthe. residual `,charge .and

depositing the same -in the reaction Another vobject is to removethecohy deposit i'romgthe reaction chamber withouty the use o! mechanical equipment. Another object istoremove f the cokedeposit in a cyclevoiloperatingi steps which provide ior accurate control ci the temperature of the-reaction chamber. Another object is to provide apparatus especiallyV adapted for high temperature operation;y f Other objects will become apparent from the detailedfdescrip- 'I'he invention involves p'rls'ing or containing residual material bi removingtherefrom any components not in vapor phase and segregating thefcomponents in th'eiorm oi'a deposit within thechamber, thereby to provide oieanvolatlle. or'v distillate material which'is directly usable or which. mayy be `subjected to anyfurther conversion, transforming or other treating operation. i Inthe kcase lo: hydrocarbonsthe Y stock isheated and while at least partly in vapor' phase vis fed to y v having substantial .heat storage capacity at a suitable rate and in such a manneras to permit charge within the cham-f components entering with 'the i=hnl'fe.l "l A'dilumt supplied-to independently of the' charge to a coking cx'I separating chamber steam o r other vaporising' iiuid increase and be permitted lhigh degree,

ing range. All or a partof the heat vreduii'ed for' @the separating treatment'will be provided by the regeneration reaction or the period ot process following the on-stream reaction wherein ythe coke from the chamber by oxidation duced is absorbed by the ychamber walls and f. other structure including Vanyy contact material which it maybe desired to inthe reaction chamber-to aidtheprocess. u l

. The oxldationof the depositv will be 'eiiected by ladmitting airor other oxygen-containing medium to the chamber arter the` endothermic on- `stream reaction has lowered the/,temperature of .the chamber to a predetermined pointes around 900 F.,xwhich is a temperature su'iiiciently high te beginl the burning of the deposit. During the burning the temperature of the chamber will for example, to ya temperature of between 1200 F. and 2000, F. After the burnhas continued for-.a period ottime determined bythe temperature to which it is desired Ato permitthechamberto rise theoxidizing medium will be cut oi! and a iluidsuch as steam will be supplied to the chamber-.where it will react at the high temperature; withany coky deposit or carbon remaining therein and produce 'HL CO and'COa in proportions dependent on the temperature oi' the chamber and the amount oi steam supplied. The reaction of 'steamwith the carbon also removes some .ci thecoky deposit and at the vsaine time cools the chamber. and the cycle of oxidation of the deposit with a regenerating medium and cooling'oi the-chamber with steam may be' repeated las often as necessary until `all or a desired" portion of the coke is removed.

After allor anyy desiredV amount of coke has beenremoved Ithe chamber will` be cooled down to atleast 13004 F. but not below 1000l Eheim beginning the ort-stream period of the cycleand Vthe an-stream "determined period. of time or so long astheichamber remains ata temperature above 900' F. Ii the stored-heat o! the exothermic reaction is insuiiicient to maintain this temperature dining operation carried out fory a prean on-streamperiod the steam or other `ciiluent mediument'ering the chamber will be sumciently to assure the supply oi krmt,percentage'of inert `r'duid suppl-ladite the coking` chamber during the ca-streamv oi the chargewill determine the v'to increase to a verw 'which consequently reduces the time of contact of the vapors in -the chamber toY give a distillate product including heavy components of up to about 95 per cent oi' the charge, which product .is-

suitable for use in a catalytic cracking without further treatment.

'Ihe coking chamber will be lined with a refractory or heat resistant material in order that high temperatures may be used. l The chamber will be maintained above 900 F. by the evolved exotheroperation mic heat of the regeneration reaction and permissibly by heat added by the superheated steam or other vaporizing huid. When a packing or contact material is used to assist the on-stream reaction more vheat can be stored in the coking chamber and the refractory wall lining may be relatively thin while if no contact material is used the refractory'linlng should be of substantial thickness to maintain the temperature of the chamber above 909 F. and to give a sumciently long on-stream reaction period to be commercially economical. Temperatures for the oni-'stream period are preferably in the range of 1090 l". to 1100 F. in order to provide for the rapidf vaporisation of the liquid material in the charge. The quantity of vaporizing' inedium supplied to the coking chamber will vary with the type of residual charging stock and for the most refractory stocks will be as high as 30 per cent by, weight f the willbesu astopermittheresidual chargeto expand therein and remain only sufficiently long to separate out the heavy components. Due to the hightemperatm'e of operation oi.' the coking chamber the other conditions are adjusted so that the time of the vapors in the coking chamber will be less than 15 seconds and for most stocks less than 5 seconds.

In order to-illustrate the invention, reference maychbe had to the accompanying drawings, in whi Fig. l is a vertical sectional view of onejorm of apparatus with certain parts appearing in elevation:

apparatus forcarrylng out the invention.

Referring to 1'18. separator casing providing a coking chamber and having upper and lower partitions Il and I2, respectively, extending `ther-escrocs forming with theupperan'd lowerendwallsof the separator a top manifold I8 and bottommanifold Il. The 'partitions ifi and il are preferably constructed of refractory material with the necessary metallic supporting materials embedded therein and form therebetween a reaction chamber generally indicated a't il, which has its top. bottom and side wallslined with 'ceramic or other heat resistant material. tion chamber contains i. body of relatively inert contact material M such as crushed quartz, fragment of brlck,.pieces of pumice, alumina. molded units of ehinaclayor othersilicates of alumina The size of .the coking chamber Pig. 2 is asimilar view 'of anotl'ieri'ormy of 1, le maintes generally a indicated generally at Il. The reecor clayey materials. The manifolds i3 and i4 are placed in communication with the `reaction two sets or series,.one ofwhichcommm'icates through the upper wall Ii with the upper lmanifold and the other set of whichvcom'municates through the lower. wall l2 with the lower manifold I l.

The upper manifold Il is placed in communication with a' pair of valved conduits i8 and I! through a interconnecting conduit 20 while the lower manifold Il ilikewise in communication with a pair of valvedconduits 2| and 22 through an interconnecting conduit 23. valved conduits 21 and Il are placed in direct communication with the reaction chamber and the various conduits may be used ln nipplyins fluid to orremoving huid from the reaction chamber. A valved conduit Il extends through the side wall of the reaction chamber and is disposed above the body of contact material for supplying hydrocarbon duit N is provided with a heater or heat exchanger 20 which is disposed exteriorly of the coking chamber and is used for heating the in' am coming charge to the desired temperature.

In operation the hydrocarbon charge is heated in the none 1l to a temperature between 800 and 900 l'. in a manner to preventany cracking oi the charge to material in the -gasoline boiling range and, in order to mist in the heating step, a conduit I. is ded anterior of the heater and in communica' n with conduit II, which is used for supplying steam or other vaporizing medium directly to the manifold I3. The amount 4; of steam mixed with the charge before entering the heating sone is dependent upon the rate or heating and the particular charging stock used which will permit the heated charge to enter the sone predominately in vapor phase with the so liquid components mixed therein. -In order to effect a rapid vaporlzation vof the liquid componente in the charge, the coking zone will be maintained at a high temperature and will not to drop below 900" F.- This temperature may be maintained at least in part by steam or other vaporixing iiuid, which is admitted directly to manifold il through conduit Il. aloneor along with steam or other vaporizing fluid which is supplied to manifold Il ,through conduit tl. w The steam4 orvaporizing duid which is admitted to the coking sone, in addition to helping to maintain the sone at its proper temperature, also asslats in vaporisation of the liquid components of the charge and eifech a rapid removal oi the ce vapors from the coking sone'through conduits 21 or 2l. During the oli-stream reaction a coky deposit will accumulate on the contact material M,

the amount from a particular charge will depend onthelengthoftheon-stream'run andthe 'lo amount 4oi' vaporising duid used during theA operation. It is benencial during the-on-stream Period to supply the vapor-Ising medium from each of the manifolds Il and Il so that all of the are preventedrrombocoming clogged due `7l to the coke depositing thereonv which mightprecharge through one or more nonies 2l. The con--` vent free newv of the'regeneruqgmedium when @s't of charge through Jconduit l24 isV stopped( in order l i l" been maintained @above-90Min;wnrbefsuppued /are in communication'vithmanifoldv I3, andf the 1 the contact material `due tothe high temperature t in the chamber, and;imeheatievolvedjwhilethe. e y burning continuesjinoreasesz'rthezztemperature off amber' preferably tangentiauybhe f y the contactmaterialzandlefractorylining sothat l f y Y .steam may be'a'dmittedthereto through kenduit 30A 8 alone. vorif desired, alongwiththeair and fthe zone'reaets wim-.the carbonT in, theeekihg ehemfss 'to' f .ber and forms Coi-COzfarid. H2 and assis "n coke depOsit alternately byaiLandisteanriyayl. vf3 bstantially ',the' entirev inner Wall lof rvthe to removetheA proper vamountof,the cokeI sit r d 'gutthrough outlet'5`2'.' 'During' the u some steamshold b e admitted v.which will permitgasatisfaotory on strearr 1 .reag Ition in the chamber. fThe oh'stre,arn reaction a `eration, has been Jvcooled down/Lto aboutllBOOjanl pera;nony may be-'qn yedytdethe onistream reactionmay eontinue untilgthe` refract riness o f'the hargeuntil v i temperature of theookingehamber downto about ,g

' 900;l When the 'onstreaml-period isrelati ly;

ruet'edof alumina; forms' a reaotiorrehainbeC positioned 'Within the casing-'in"afrnai1`rier-v d swithftheinner w@ 1scfftne 'f y eehargefifs admitted'through*con-,rV to regenerate the ookingjjpharnber gnderemo've duit 42-f having` `heater? 43`associatedftlfierevif4 hg any desired amountof deposited oke; lAfter-the 'lr'ifold is provided f'i"e'on'veysupply vof heated charge isfstobpe'd'stemorother: 'fluidlsoh asfstamtothe j inert gas is Vsubplied 'tothefoking cha'rriber in ,`f42. tlf ugh valved conneetionf`45`f order tofpurge the conta'otmateriallof 'anyliquid I i direotly' to hereaction chamber -C throgh remaining therein Jandthfvalves'rini)conduits 2l l0 valvedfeordui "46. 'f Aheader 41 vis i'ced'litvvarde' f and r28 will 'remain'openfdringthepurge'period` f to remove purgeproducts's TAt'lthe beginning -of the regeneration the oking 'zone 15', whichfhas After' the deafeningstream vperiod'thesiflppiyf'f with air from vconduit'.` li'and thetubesill which 'j v f be nl oY munioationwith the space S fq'rredby marninous tube 41 to distribute fluidievely y air will Vvpassin-parallel iowiacrossfthefeontactl "againlsjtliefouter Wall 'ofthe'tube `Valve inlet f Y materialto the -set oftube's I1" whiohdare in,com'.` A n "cti ns150 afd l'jarey infcommunic'ato with er 4for respectively supplying air hd theh'eader for passage 'into thes"1`ja e';5.1 peration 'of 'this oking 'Chamber fftiie" ook is'treated under'oonditions" similar v f plainediin'the operation ofjth'efapp'- l Abut will be admittedfat the air or other oxygen-'containing medium effects ai'i'.VVA he' immediate oxidationor burning of the lcoke from the coking zone mayv reach ya 'temperature-.as high as 1800 or 2000"-dependingon the degree v 90031@1 'and steam or vaporizine Huid will of burning; In-order ,;tocoo1` the ticking-chamber.

agi to the chamber in an ar'ountnec's Y' dependent kon the particular v'cha'.r'ge."to ini" hej'vaporiziation of the liquid portion'of harg' and to limit the time'of Contact 'of rsnnfthel chamber to less'fthan'1-5`secthisforr'n of vapparatus the'c'oke" tends jthewalls'oflthe chamber anclthrate Eming charge and amount "ofV v'vaporiz'ing 'controlled so that thecoke is deposited 1S temperature brought down, .to'.thatj desired to` I start; the succeeding.onestreamgreaoti .-fljhe y 2f Y steam, in addition `tocoolinggdoyvn the, cking i u un ih removing the coke depositi The removaLo 'the H fluidi from becoming 'eloggoke 1' be started whenagthejcoking chamber; i Itch-rege@ heatvused up during'this reaotuion has reduced[they gort this reactionLmay*beieearridiout sole t e heat stored inthe cok'ng -chambex'durin d regenerationl raeti'onr. Y n In case the ookeffdistr'ibutio'n 'irrthe packed .casey gives uneven :heating ori-regeneration the tem--v per'ature .cammini-the chamber een be effected f f by a'proper distribution of air adfsteamithrough 1 Aroughv valved connection, 'ffor jets 149. "The removalyofjooke by the alternate adissionfot la'i'nedV heavier Ycarbondepositis formedatthertop ofthe i y mass than at thebottom large amounts gofvsteam@ n canv be admitted through conduit 21. vto theftopoiv, the mass and less sizean'- admittedthrough oo nff duit' 28 in order tove'ontrolf the .temperature and@ d maintain allv portions ofthe mass ata substan-j` tiallyv vuniformtemperature.' 1In,some-types of y y y regeneration it` may-'beladvantargeous,to supply d air at Oneof the conduits 'f2-'Lor 28*or,-:bothf'ands 1.,' remove the regenerationproduotsthroughmani#- v te folds I3 and I4: "1 ',g .I r1," Fig. 2 is representative offa difierent'orv` atleast a. modified form ofapparatus Whichfmaybejused- Y to perform the process of the-invention. It com'- :10 y at an averagetemperaturgjef prises a ceramic-casing generally indicated at 40, aboutfilOOOj n yvaporized portion 9f the having side and end wallsiof substantial thickcharge was Withdrawn rapidly from the chamber. ness in order to retain sufcient heat in [the Byeontrollingithe rate of feed of the `charge to chamber for an ontream reaction.` Aforarni--- the chamber ,and-j: regulating thek percentage, of nous enlarged tube 4|,ifwhich preferably viscon-s'll steam or vaporizinggnuid entering the chamber through the chambe an'dother `g`, the chamber jthe `enamthe vapors were removed therefrom in about-l5 seconds. Recovered liquid boiling abovethe gasoline` boiling range comprised about 853.7pe`,r cent ofthecharge While the coke` deposited ,in the chamber was very small, being `slightly less .than

Y 5 .per cent byweight of the originalcharge and the. amount of gasoline formedwas vaboutlO per cent ofthe charge. In another ,operationon the 'samecharge and with all other'fconditions of operation the same excepting the percentage ,of

steam ,used which was increased tp reducethe Contact Vtime of the vapors in the chamberto about 5 seconds, the coke deposit remainedabout thesame or about 5 per cent of the kcharge-while the gasoline production was decreasedtofabout 5 I claim as myinvention: 1. Ina cyclicprocess involving alternate enxdotherrnic andxothermi'c'reaction periods for vtreating a liquid or-liqueilable heavy hydrocar- Vbon charge to remove, tarry and coky material therefrom randproducea. clean distillate stock,

the steps of heating the Vcharge to atemperature per-centand the liquid boiling above-thegasoline boiling range increased about 5 per cent.v -Sube stantially the same results are obtained .with either type of apparatus illustrated. I, It is apparent from these typical operations that `.a high recovery of liquid product-boiling 1 `above the gasoline boiling rangecanabeobtained with the production of a very low percentage vof coke.; l It is also apparent that theprocess can be operated to minimize gasolineformation by reducing the vapor time of contact yin the. vcllarriber in order to remove the vapors from tliechamf -ber before they have time to crack to gasoline.

The contact time is the resultant of. the tem'- perature, pressure and size of chambenfasjwell as the type of chargingstock, rate of feed .ofthe charging stock to the chamber, and thel 'per- .centage of vaporizing fluid entering ythe chamber.

The contact time of any particular operation can be arrived at from the volume of vapors, leaving,

the chamber. lThe vapors leavingthechambefr will be steam, fnon-condenslble,gasesaad oil. The volume of steam at the temperature y,and pressure conditionsv of the chamberfcanbe caldensible gases can be calculated from tl'ieme't'lio'd outlined for perfect gas laws. 'I'he,y volume of vaporized oil can be calculated, for' example, from publication #97 of the Bureau orV Sgtandardfseentitled Tvhermal Properties of Petroleum; ucts in which are given calculatedr'value' minedv for different petroleumzffactionst contact time given for the opera'tionslovngthe `6 5,

per cent bottoms of Southern California fueloil has been` determined as above explained."

be carried out readily With eithertype of coking apparatus shown. However, with. alj'charge con-` taining La. high percentage of liquid it yvilljbe found ,advantageous to use the'pacited chamber 0f Fig 1 since the heat stora'gecapaoity will be greater than that of an unpacked p chamber and r.The general process stepsof the'inventio'n thehighertemperatures will of iconrse'eifect a more rapid'vap'orization of thel liquid. `"For treating charges containing a smallpercentage 'of Aliquid or f orsmall scale operations the unpacked chamber of Fig. 2 wm adeqaatew Servei 't0 0b.

tain optimum results. Anyrijconventional vordesired -forms of balling members maybe provided overA connections used as outlets `'forth'e reaction l chamber (such as 21 in Fig; l`1orj52 inFig. 2) `to prevent entrainment of liquids'jorfsolidswithoutgoing vapors.

The invention isnot to be l a tions orl examples but is inten ed'to includeall modifications within the scopfofthe appended claims. l i

limiten by illustraabove 800 F. to provide'fa mixture `of vaporized material and unvaporized liquid material and under Aconditions to.A prevent anyV substantial cracking of the mixture into lower boiling hydrocarbonsof .the gasoline type, feeding the heated mixture kduring they-endothermic period to a reqfractory separating zonehaving substantial heat -storage capacity after aniexothermic reaction has charge to the separating zone to effect removal of the vaporlzed material from the zone in less than 15 seconds inorder tof prevent any substantial amount of crackingto gasoline while retaining the coke in the zone, then cutting off the supply of the heated-mixture tothe zone during `'a succeedingV exotherr'rilc period and coke 'from the zoneby burning'. f 2. Inra cyclidprocess' involving alternate endoremoving 'thermic and 4'exothermic lreaction periods for rtreatinga liquid or llqueable heavyfhydrocarbon chargeto ren'iove'ta'rry` and coky material therefrom and'produce afclean `distillate stock, the steps of heating the charge-to a temperature above 800 F. toprovide a mixture yof vaporized 'material 4and unvaporiz'ed liquid material and "under"T conditions to prevent rany substantial cracking of themixtur'e into lower boiling hydro- Ycarbons of the gasoline type, feeding the heated mixture during theendothermic period to a reiractory separating zone havingV substantial heat storage capacity afteri 'ad exothermic reaction had'fbeen 'conducted inxthearefraotory zone to removetherefromfcoky deposit and wherein duri'ng" 'the' exoth'ermic 'reaction' the I temperature of the zone had gone above .1100? F. and sufeient heat had'beenstoredin the1zoneto maintain the zone above 900 F.;during-theendothermic period of operation in `order toeect withinthe zone rapid" decomposition'iof` the liquid material into Vaporized material boiling above the gasoline boiling range and coke, controlling the feeding of the charge tothe separating zone to effect removal of the "vaporized material from the zone in less than 15 secondsgin order to prevent any substantial amountof cracking to gasoline while retaining Vthe coke in the zone,.then cutting off the supply of the heatedmixture to the zone during a succeeding exothermic period and removing 'coke from the zone-by supplying an oxygen containing medium to effect burning ofy the coke until the zone rises in temperature above 1300 F., supplying steam to the zone to remove more coke and effect a-cooling of the zone to the temperature desirable to begin the endothermic reaction. v JOHN R. BATES. 

